US20240216896A1 - Catalyst containing phosphorus and sodium and use thereof in a hydrodesulfurization process - Google Patents

Catalyst containing phosphorus and sodium and use thereof in a hydrodesulfurization process Download PDF

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US20240216896A1
US20240216896A1 US18/286,642 US202218286642A US2024216896A1 US 20240216896 A1 US20240216896 A1 US 20240216896A1 US 202218286642 A US202218286642 A US 202218286642A US 2024216896 A1 US2024216896 A1 US 2024216896A1
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catalyst
sodium
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Antoine FECANT
Etienne Girard
Philibert Leflaive
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IFP Energies Nouvelles IFPEN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • Petroleum refining and also petrochemistry are now subject to new constraints. This is because all countries are gradually adopting strict sulfur specifications, the objective being to achieve, for example, 10 ppm (by weight) of sulfur in commercial gasolines in Europe and in Japan.
  • the problem of reducing sulfur contents is essentially focused on gasolines obtained by cracking, whether catalytic (FCC, Fluid Catalytic Cracking) or non-catalytic (coking, visbreaking, steam cracking), the main precursors of sulfur in gasoline pools.
  • FCC Fluid Catalytic Cracking
  • non-catalytic coking, visbreaking, steam cracking
  • hydrodesulfurization catalysts which are both active in hydrodesulfurization and also very selective for hydrodesulfurization relative to the olefin hydrogenation reaction.
  • document EP0736589 is known from the prior art and discloses a process for the hydrodesulfurization of an olefinic gasoline cut containing sulfur implemented in the presence of a catalyst comprising an active phase based on at least one group VIB metal and at least one group VIII metal on an alumina-type support, said support additionally containing an alkali metal in a content range of between 0.2 and 3% by weight relative to the support.
  • the support may also comprise another compound chosen from boron, phosphorus and silicon, although the contents thereof are not disclosed.
  • the total content of group VIII element is between 0.5 and 10% by weight of oxide of said group VIII element relative to the total weight of the catalyst.
  • the phosphorus content is between 0.1 and 10% by weight of P 2 O 5 relative to the total weight of catalyst.
  • the molar ratio between the group VIII element and the group VIB element is between 0.1 and 0.8.
  • the molar ratio between the group VIII element and the sodium, calculated on the basis of the content of the group VIII element and of the sodium content, relative to the total weight of the catalyst is between 2 and 400.
  • the total pore volume is measured by mercury porosimetry according to the standard ASTM D4284-92 with a wetting angle of 140°, for example using an Autopore@ III model device of the Micromeritics® brand.
  • group VIII, group VIB and group V elements are measured by X-ray fluorescence and by inductively coupled plasma spectrometry (ICP) for sodium. 15
  • the group VIB element is preferentially chosen from molybdenum and tungsten, more preferentially molybdenum.
  • the group VIII element is preferentially chosen from cobalt, nickel and the mixture of these two elements, more preferentially cobalt.
  • the total content of group VIII element is generally between 0.5 and 10% by weight of oxide of the group VIII element relative to the total weight of the catalyst, preferably between 0.8 and 9% by weight, very preferably between 0.9 and 6% by weight of oxide of the group VIII element, relative to the total weight of the catalyst.
  • the element content is expressed as CoO or NiO, respectively.
  • the group VIB element content is generally between 1 and 30% by weight of oxide of the group VIB element relative to the total weight of the catalyst, preferably between 2 and 20% by weight, very preferably between 4 and 15% by weight of oxide of the group VIB element, relative to the total weight of the catalyst.
  • the metal content is expressed as MoO 3 or WO 3 , respectively.
  • the support of the catalyst according to the invention can be synthesized by various methods known to those skilled in the art, for example by rapid dehydration of a precursor of aluminum trihydroxide (Al(OH) 3 ) type (otherwise known as hydrargillite or gibbsite) for example from the process commonly called “Bayer”.
  • a shaping is then carried out, for example by granulation, then a hydrothermal treatment and finally a calcination which leads to the obtaining of alumina.
  • This method is notably described in detail in the document by P. Euzen, P. Raybaud, X. Krokidis, H. Toulhoat, J. L. Le Loarer, J. P. Jolivet and C.
  • the tungsten precursors which can be used are also well known to those skilled in the art.
  • use may be made, among the sources of tungsten, of the oxides and hydroxides, tungstic acids and salts, in particular the ammonium salts, thereof, such as ammonium tungstate or ammonium metatungstate, phosphotungstic acid and salts thereof, and optionally silicotungstic acid (H 4 SiW 12 O 40 ) and its salts.
  • the sources of tungsten can also be any heteropolycompound of Keggin, lacunary Keggin, substituted Keggin or Dawson type, for example.
  • Use is preferably made of the oxides and the ammonium salts, such as ammonium metatungstate, or the heteropolyanions of Keggin, lacunary Keggin or substituted Keggin type.
  • the sodium can advantageously be introduced into the catalyst at various stages of its preparation and in various ways. It can advantageously be introduced alone or as a mixture with at least one of the group VIB and group VIII elements and phosphorus.
  • Any source of sodium known to those skilled in the art can be used.
  • the source of sodium is sodium nitrate, sodium chloride, sodium hydroxide, or even sodium sulfate.
  • TH200@ alumina sold by Sasol® 100 grams are calcined in a fixed traversed bed at 750° C. for 4 hours under an air flow of 1l/h/g.
  • the support S1 thus obtained has a specific surface area of 90 m 2 /g, a pore volume measured by mercury porosimetry of 0.60 ml/g and a loss on ignition of 2.6% by weight.
  • the impregnation solution is prepared by dissolution at 90° C. of molybdenum oxide (2.25 g, purity ⁇ 99.5%, Sigma-AldrichTM), cobalt hydroxide (0.61 g, purity 99.9%, Alfa Aesar®), phosphoric acid at 85% by weight (0.51 g, purity 99.99%, Sigma-AldrichTM) in 15.6 ml of water.
  • molybdenum oxide 2.25 g, purity ⁇ 99.5%, Sigma-AldrichTM
  • cobalt hydroxide (0.61 g, purity 99.9%, Alfa Aesar®
  • phosphoric acid at 85% by weight (0.51 g, purity 99.99%, Sigma-AldrichTM
  • the Co/Mo and P/Mo molar ratios are respectively 0.40 and 0.28.
  • the P/Na molar ratio of catalyst A is 306.
  • the Co/Na and Mo/Na molar ratios are 436 and 1082 respectively.
  • Example 2 Catalyst B (not in Accordance with the Invention)
  • the Co/Mo and P/Mo molar ratios are respectively 0.40 and 0.
  • the P/Na molar ratio of the catalyst is 0.
  • the Co/Na and Mo/Na molar ratios are 10 and 25 respectively.
  • the catalyst support D is also the support S3. Cobalt, molybdenum and phosphorus are then added.
  • the impregnation solution is prepared by dissolution at 90° C. of molybdenum oxide (2.2 g, purity ⁇ 99.5%, Sigma-AldrichTM), cobalt hydroxide (0.60 g, purity 99.9%, Alfa Aesar®), phosphoric acid at 85% by weight (0.48 g, purity 99.99%, Sigma-AldrichTM) in 14.9 ml of water.
  • molybdenum oxide 2.2 g, purity ⁇ 99.5%, Sigma-AldrichTM
  • cobalt hydroxide 0.60 g, purity 99.9%, Alfa Aesar®
  • phosphoric acid at 85% by weight
  • Sigma-AldrichTM phosphoric acid at 85% by weight
  • the Co/Mo and P/Mo molar ratios are respectively 0.40 and 0.28.
  • the P/Na molar ratio of the catalyst is 7.3.
  • the Co/Na and Mo/Na molar ratios are 10 and 26 respectively.
  • Example 5 Evaluation of the Performances of Catalysts a to D Used in a Hydrodesulfurization Reactor
  • the performances of catalysts A to D are evaluated in the hydrodesulfurization of a catalytic cracking gasoline.
  • a model feedstock representative of a catalytic cracking (FCC) gasoline containing 10% by weight of 2,3-dimethylbut-2-ene and 0.33% by weight of 3-methylthiophene (i.e. 1000 ppm by weight of sulfur in the feedstock) is used for the evaluation of the catalytic performance of the various catalysts.
  • the solvent used is heptane.
  • HSV volume flow rate of feedstock/volume of catalyst
  • H 2 /feedstock volume ratio 300 SI/I
  • Each of the catalysts is placed successively in said reactor. Samples are taken at different time intervals and are analyzed by gas chromatography so as to observe the disappearance of the reactants and the formation of the products.
  • the catalytic performance of the catalysts is evaluated in terms of catalytic activity and of the selectivity.
  • the hydrodesulfurization (HDS) activity is expressed from the rate constant for the HDS reaction of 3-methylthiophene (KHDS), standardized by the volume of catalyst introduced, and assuming first-order kinetics with respect to the sulfur-comprising compound.
  • the olefin hydrogenation (HydO) activity is expressed from the rate constant for the hydrogenation reaction of 2,3-dimethylbut-2-ene, standardized by the volume of catalyst introduced, and assuming first-order kinetics with respect to the olefin.
  • the selectivity of the catalyst is expressed by the standardized ratio of the rate constants kHDS/kHydO.
  • the kHDS/kHydO ratio will increase as the catalyst becomes more selective.
  • the values obtained are standardized by taking the catalyst A as reference (relative HDS activity and relative selectivity equal to 100). The performance qualities are thus the relative HDS activity and the relative selectivity. The results are listed in table 1 below.
  • Catalysts A B C D (not in (not in (not in (in accordance) accordance) accordance) accordance) Catalyst Na 2 O 20 4500 850 840 content (ppm) P/Na molar 306 1.4 0 7.3 ratio Co/Na molar 436 1.9 10 10 ratio Mo/Na 1082 4.8 25 26 molar ratio Co/Mo 0.40 0.40 0.40 0.40 molar ratio P/Mo 0.28 0.28 0 0.28 molar ratio Relative 100 82 114 130 activity Relative 100 106 76 108 selectivity
  • catalyst D according to the invention exhibits better performance in terms of activity and selectivity compared to non-compliant catalysts A, B and C and therefore underlines the importance of an adjusted Na 2 O content in the catalyst and of the specific and optimized P/Na molar ratio in order to obtain improved performance in a gasoline hydrodesulfurization process.
  • This improvement in selectivity of the catalysts is particularly advantageous in the case of use in a process for the hydrodesulfurization of gasoline containing olefins for which it is sought to limit as much as possible the loss of octane due to the hydrogenation of the olefins.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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US18/286,642 2021-04-21 2022-04-15 Catalyst containing phosphorus and sodium and use thereof in a hydrodesulfurization process Pending US20240216896A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FRFR2104145 2021-04-21
FR2104145A FR3122105B1 (fr) 2021-04-21 2021-04-21 Catalyseur contenant du phosphore et du sodium et son utilisation dans un procede d’hydrodesulfuration
PCT/EP2022/060158 WO2022223482A1 (fr) 2021-04-21 2022-04-15 Catalyseur contenant du phosphore et du sodium et son utilisation dans un procede d'hydrodesulfuration

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EP0586196A1 (en) * 1992-09-01 1994-03-09 JOSEPH CROSFIELD & SONS LTD. Silicone modified hydrotreating catalysts
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US8258074B2 (en) 2005-03-24 2012-09-04 Intevep, S.A. Hydroprocessing of naphtha streams at moderate conditions
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AU2022260439A1 (en) 2023-10-05
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